The present invention relates to anhydrous cosmetic makeup compositions comprising a fatty phase and a cosmetic treatment process using these compositions.
Known anhydrous cosmetic compositions comprise a fatty phase containing mineral or organic oils, fatty bodies, surfactants intended to provide a homogeneous phase and, most often, waxes. Dyes and pigments are added when it is desired that the anhydrous composition be colored.
Anhydrous cosmetic makeup compositions, such as a lip rouge, an eyelid shadow, a molded complexion foundation, and a molded cheek rouge, have as a principal purpose the application of dyes and pigments to the skin, in an even, homogeneous and durable manner.
Moreover it is known to employ cosmetic and/or dermopharmaceutical compositions which function to treat the skin on topical application thereto.
The exigencies of modern life have necessitated efforts to simplify cosmetic treatments by using cosmetic compositions having several functions thereby reducing the number of required cosmetic treatment operations.
These efforts have involved the introduction in the anhydrous makeup compositions of cosmetic and/or dermopharmaceutical active materials. To this end, efforts have been made to introduce lipophilic active materials which can be dissolved in the fatty phase of the anhydrous compositions. This fatty phase often contains a large amount of wax and its absorption by the skin or the mucous membrane is very limited. Consequently, the effectiveness of the active materials, which is a function of the penetration of the fatty phase in the skin, is also quite limited.
Consideration has also been given to introducing water-soluble active materials. However, their introduction requires costly technological measures such as the lyophilization of the active materials, then their microdispersion in the fatty phase or the incorporation of the active materials in solid supports such as microspheres or microcapsules and then their dispersion in the fatty phase. In this latter case, the amount of active material that can be introduced is limited because the incorporation of solid supports, containing the active materials, modifies in a significant manner the mechanical properties of the anhydrous compositions.
Thus, until now, the problem of introducing cosmetic and/or dermopharmaceutical active materials into anhydrous cosmetic compositions has not been resolved in a satisfactory manner.
This problem also exists in the case of anhydrous cosmetic products such as deodorant sticks and anhydrous anti-circle compositions.
On the other hand, it is known that certain ionic or non-ionic amphiphilic lipids and certain mixtures of amphiphilic lipids are capable, on contact with an aqueous phase, of forming vesicles constituted by more or less spherical lamina of the vesicular lipidic phase, encapsulating an aqueous phase.
In a known manner additives can be introduced into the vesicular lipidic phase to improve the stability and the permeability of the resulting vesicles. These additives can be sterols, and in particular, cholesterol or dicetylphosphate.
In the present application and in the claims, the term xe2x80x9cprovesicular lipidic phasexe2x80x9d designates amphiphilic lipids capable of forming vesicles, mixtures of ionic and/or nonionic amphiphilic lipids capable of forming vesicles and amphiphilic lipids or mixtures of amphiphilic lipids containing additives to improve the stability and permeability of the resulting vesicles.
It is well known that these vesicles already possess, in themselves, a cosmetic activity on topical application but especially that they permit the encapsulation of water-soluble and liposoluble cosmetic and/or dermopharmaceutical active materials in the lipidic and/or aqueous phase. The preparation of vesicles from amphiphilic lipids and their use in cosmetics are, for example, described in French application 2,315,991.
Moreover it is known from FR A 2,416,008, that the lipidic vesicles can be lyophilized and that after lyophilization these vesicles retain their treating characteristics. From this one conclusion would be to introduce lyophilized liposomes and/or niosomes into anhydrous cosmetic makeup compositions. But this operation is complicated and costly on the industrial level, for it requires producing vesicles from amphiphilic lipids, lyophilizing them in the presence of anti-agglomerating agents and/or cyroprotectors having no particular advantage for cosmetic compositions, and then to incorporate them at an elevated temperature in a complex cosmetic product containing melted oils and waxes.
According to the present invention the applicants have found that the provesicular lipidic phase, capable of forming vesicles in the presence of water, retains its ability to form vesicles when it is mixed with a fatty phase, generally employed for the production of anhydrous cosmetic compositions, which fatty phase contains organic and/or mineral oils, fatty bodies, and most often, waxes and surfactants.
In effect, as shown in the comparative examples given below, that after contact with water, the formation of vesicles in the aqueous phase of satisfactory quality and significant quantity is observed. Moreover, it is noted that the resulting vesicles retain their capacity to encapsulate hydrophilic and/or lipophilic active materials and that under these circumstances the effectiveness of the active material, introduced into the anhydrous composition, is very clearly improved.
It was not obvious to the skilled artisan that when the provesicular lipidic phase, capable of forming vesicles in the presence of water, was mixed with the fatty phase, employed in the production of anhydrous cosmetic makeup compositions, it would again be possible by mere contact with an aqueous phase, to form vesicles therein. In particular, it was feared that, when the provesicular lipidic phase which is constituted of a mixture of ionic amphiphilic lipids and/or non-ionic amphiphilic lipids or amphiphilic lipids combined with one or more additives, the combination of these different compounds, which can be required for the formation of vesicles in a stable form, would be destroyed by the oils, fatty bodies, waxes and the surfactants contained in the fatty phase of the anhydrous cosmetic product.
According to the present invention this discovery is utilized in the production of anhydrous cosmetic compositions containing in the fatty phase, a provesicular phase capable of forming vesicles on contact with water, these anhydrous cosmetic compositions being contacted with an aqueous phase at the time of their use to cause the formation of vesicles.
It is necessary to note that the contact with an aqueous phase is most often inherent in the method of application of these anhydrous cosmetic compositions.
For example, lip rouges are contacted with the labial mucous membrane, which is rich in water, and which is regularly moistened by the saliva; molded complexion foundations, eyelid shadows or cheek rouges are often hydrated just before application using a wet sponge; deodorant sticks are applied to the skin which is moistened by sweat secretions.
The present invention thus-relates to an anhydrous cosmetic composition comprising a fatty phase which is characterized by the fact that the fatty phase contains a provesicular lipidic phase containing at least one amphiphilic lipid capable of forming vesicles on contact with an aqueous phase.
Preferably, the cosmetic composition contains a water-soluble and/or liposoluble cosmetic and/or dermopharmaceutical active material.
The amount of the provesicular lipidic phase containing the amphiphilic lipids can represent from 0.1 to 30 percent by weight of the anhydrous composition, preferably from 1 to 20 percent.
In the provesicular lipidic phase, the amphiphilic lipids employed can be any amphiphilic lipid known for the production of vesicles in the presence of water. These lipids are, in a known manner, amphiphilic lipids of natural or synthetic origin, ionic or nonionic, having, per molecule, one or more long chain, saturated or unsaturated, linear or branched hydrocarbon chains, having preferably 8 to 30 carbon atoms. These chains are, for example, oleic, lanolic, tetradecylic, hexadecylic, isostearylic, lauric or alkyl phenyl chains, and one or more hydrophilic groups taken from hydroxyl, etheroxide, carboxyl, phosphate and amine groups.
Preferable ionic amphiphilic lipids include natural phospholipids (for example, egg lecithin or soy lecithin or sphingomyelin), synthetic phospholipids (for example, dipalmitoylphosphatidylcholine or hydrogenated lecithin). Amphoteric lipids having two lipophilic chains or a combination of two organic ions having a long chain of opposite signs can also be employed, as can anionic lipids.
Among the ionic amphiphilic lipids mention can be made of those which are described in Luxembourg parent application 85 971, filed on Jun. 23, 1985, and which are represented by the formula: 
wherein
R1 represents C7-C21 alkyl or alkenyl,
R2 represents a C7-C31 saturated or unsaturated hydrocarbon radical, and
M represents H, Na, K, NH4 or a substituted ammonium ion derived from an amine and, principally a hydroxylated amine.
Preferable nonionic amphiphilic lipids include those containing, as hydrophilic groups, polyoxyethylenated or polyglycerolated groups, or groups derived from esters of polyols oxyethylenated or not, or even hydroxyamide derivatives. Advantageously, the nonionic amphiphilic lipids are selected from the group consisting of:
(1) linear or branched polyglycerol derivatives having the formula
R3"Brketopenst"C3H5(OH)O"Brketclosest"{overscore (n)}Hxe2x80x83xe2x80x83(II)
wherein
xe2x80x94C3H5(OH)Oxe2x80x94 is represented by the following structures taken separately or in admixture:
xe2x80x94CH2xe2x80x94CHOHxe2x80x94CH2Oxe2x80x94, 
{overscore (n)} has a statistical average value ranging from 1 to 6,
R3 represents:
(a) a linear or branched, saturated or unsaturated aliphatic chain containing from 12 to 30 carbon atoms; or hydrocarbon radicals of lanolin alcohols;
(b) R4CO wherein R4 is a linear or branched aliphatic radical containing 11 to 29 carbon atoms; and
(c) R5"Brketopenst"OC2H3(R6)"Brketclosest" wherein R5 has the meaning (a) or (b) given for R3; xe2x80x94OC2H3(R6)xe2x80x94 is represented by the following structures taken separately or in admixture: 
wherein R6 has the meaning (a) given above for R3,
(2) polyglycerol ethers, linear or branched, having two fatty chains;
(3) polyoxyethylenated fatty alcohols;
(4) polyoxyethylenated sterols and phytosterols;
(5) ethers of polyols;
(6) esters of polyols oxyethylenated or not and, in particular, esters of polyoxyethylenated sorbitol;
(7) glycolipids of natural or synthetic origin, for example the cerebrosides;
(8) polyglycerolated xcex1-diols;
(9) hydroxyamides represented by the formula: 
wherein
R7 represents a C7-C21 alkyl or alkenyl radical,
R8 represents a saturated or unsaturated C7-C31 hydrocarbon radical;
COA represents one of the following two groups:
(a) 
wherein B is a mono or polyhydroxylated alkyl derived from a primary or secondary amine and R9 represents hydrogen, methyl, ethyl or hydroxyethyl, and
(b) COOZ wherein Z represents the residue of a C3-C7 polyol; and
(10) the ethers and esters described in French patent application 90 13139 filed on Nov. 14, 1990 and having the formula 
wherein
A represents xe2x80x94OR or 
wherein R represents a saturated or unsaturated hydrocarbon radical, and
n is 2 or has a statistical average value {overscore (n)} greater than 1 and at most 6.
Preferably R represents a C7-C22 linear alkyl, a C7-C36 branched alkyl, a C18 alkenyl or alkylaryl having a linear or branched C7-C16 alkyl chain. In the alkyl aryl radical, the aryl group is, preferably, phenyl. The alkenyl radical advantageously is an octadecene-9 yl or an octadecanediene-9,12 yl group.
In a known manner, various additives can be combined with the amphiphilic lipids to modify their stability and permeability. In this regard mention can be made of the optional addition of long chain alcohols and diols; sterols such as, for example, cholesterol and xcex2-sitosterol; long chain amines and their quaternary ammonium derivatives; hydroxyalkylamines; polyoxyethylenated fatty amines; esters of long chain aminoalcohols, their salts and quaternary ammonium derivatives; phosphoric esters of fatty alcohols in free or neutralized form such as, for example, sodium dicetylphosphate and alkyl sulfates such as, for example, sodium cetyl sulfate; ionic derivatives of sterols; and certain polymers such as polypeptides and proteins.
As explained above, in accordance with the invention, there can be introduced into the fatty phase, cosmetic and/or dermopharmaceutical active materials. According to the present invention, only active materials known to have a cosmetic and/or dermopharmaceutical activity on topical application and capable of being encapsulated in amphiphilic lipid vesicles can be employed.
Representative lipophilic active materials include, principally, vitamin E, esters of vitamin E, polyunsaturated fatty acids, vitamin F, sunscreen agents, antioxidants, preservatives, vitamin A, retinoic acid and its esters.
Representative water-soluble active materials include, preferably, those which permit, on admixture with the provesicular lipidic phase the production of anhydrous lamellar phases, such as glycerol, sorbitol and other polyols having a close structure. Also useful are amino acids such as arginine, lysine, proline and serine; vitamins such as D,L-panthenol; and sunscreen agents.
In a known manner the fatty phase comprises fatty bodies such as cocoa butter and oils. Representative oils capable of being employed in accordance with the invention include, particularly:
mineral oils such as paraffin oil, petrolatum oil and oils having a boiling point between 310 and 410xc2x0 C.,
oils of animal origin, such as perhydrosqualene,
vegetable oils such as sweet almond oil, calophyllum oil, palm oil, avocado oil, jojoba oil, olive oil, ricin oil and cereal germ oils, such as wheat germ oil,
silicone oils such as dimethylpolysiloxane,
synthetic esters such as purcellin oil, butyl myristate, isopropyl myristate, cetyl myristate, isopropyl palmitate, butyl stearate, hexadecyl stearate, isopropyl stearate, octyl stearate, isocetyl stearate, decyl oleate, hexyl laurate, propylene glycol dicaprylate and di-isopropyl adipate,
organic alcohols such as oleic alcohol, linoleic alcohol, lanolenic alcohol, isostearyl alcohol and octyl dodecanol, and
esters derived from lanolic acid such as isopropyl lanolate and isocetyl lanolate.
Other oils that can also be employed include acetyl glycerides, the octanoates and decanoates of alcohols and polyalcohols, such as those of glycol and glycerol, ricinoleates of alcohols and polyalcohols such as those of cetyl.
Most often waxes are also employed and representative waxes, employed in the present invention, include:
mineral waxes such as microcrystalline waxes, paraffin waxes and petrolatum waxes,
fossil waxes such as ozokerite, montan wax,
waxes of animal origin such as beeswax, spermaceti, lanolin wax, derivatives of lanolin such as lanolin alcohols, hydrogenated lanolin, hydroxylated lanolin, acetylated lanolin, lanolin fatty acids, and acetylated lanolin alcohol,
waxes of vegetable origin such as candelilla wax, Carnauba wax, and Japan wax,
hydrogenated oils, solid at 25xc2x0 C., such as hydrogenated ricin oil, hydrogenated palm oil, hydrogenated tallow and hydrogenated cocoa oil,
fatty esters, solid at 25xc2x0 C., such as propylene glycol monomyristate and myristyl myristate.
Among other waxes, mention can be made of cetyl alcohol, stearyl alcohol, mono-, di- and triglycerides solid at 25xc2x0 C., stearic monoethanol amide, colophane and its derivatives such as glycol and glycerol abietates, sucroglycerides and the oleates, myristates, lanolates, stearates and dihydroxystearates of calcium, magnesium, zinc and aluminum.
Pigments are introduced when the cosmetic composition must be colored.
Generally there are also added surfactant agents such as succinylglycerides, alkylphosphates, esters of fatty acids such as polysorbates sold under the trade name xe2x80x9cTWEENxe2x80x9d by ICI Americas and esters of polyethyleneglycol such as those sold under the name xe2x80x9cBRIJxe2x80x9d, by ICI.
The anhydrous cosmetic composition, according to the invention, is prepared by mixing the various components. Preferably, the materials constituting the fatty phase and the materials constituting the provesicular lipidic phase are mixed separately. Then the resulting two phases are mixed until a homogeneous preparation is obtained. In this latter case the cosmetic and/or dermopharmaceutical active materials are preferably introduced into the-provesicular lipidic phase.
The present invention also relates to a process for the cosmetic treatment of the skin characterized by the fact that the anhydrous cosmetic composition, described above, is applied to the skin, the cosmetic composition being in contact with an aqueous phase when it is applied to the skin.
According to the invention, the contact of the anhydrous cosmetic composition with an aqueous phase can be effected just before application of the composition onto the skin. In this situation the composition can be removed with a wet sponge and the composition is spread on the skin using this sponge.
Contact can also be effected by spreading the composition on skin previously moistened either with saliva or perspiration, or by the water contained in the mucous membranes, or using an aqueous phase derived from an external source.
Contact can also be effected after application of the anhydrous cosmetic substance. In this case also, the aqueous phase can be constituted by perspiration or saliva or provided from an external source.
The objectives, characteristics an advantages of the present invention will appear more clearly from the examples given below as an illustration and without any limitation.